CA1223100A - Process for production of 4-methyl-1-pentene polymer or copolymer - Google Patents
Process for production of 4-methyl-1-pentene polymer or copolymerInfo
- Publication number
- CA1223100A CA1223100A CA000453668A CA453668A CA1223100A CA 1223100 A CA1223100 A CA 1223100A CA 000453668 A CA000453668 A CA 000453668A CA 453668 A CA453668 A CA 453668A CA 1223100 A CA1223100 A CA 1223100A
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- CA
- Canada
- Prior art keywords
- titanium
- polymerization
- catalyst component
- methyl
- pentene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/904—Monomer polymerized in presence of transition metal containing catalyst at least part of which is supported on a polymer, e.g. prepolymerized catalysts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A B S T R A C T
A process for producing a polymer or copolymer of 4-methyl-1-pentene, which comprises polymerizing 4-methyl-1-pentene or copolymerizing 4-methyl-1-pentene with up to about 20 mole % of an olefin having 2 to 20 carbon atoms in the presence of a catalyst comprising (A) a solid highly active titanium catalyst component composed of magnesium, titanium, halogen and a diester of a dicarboxylic acid, (B) an organoaluminum compound, and (C) an organosilicon compound represented by the following formula R13Si(OR2) wherein each of R1 and R2 represents a hydrocarbon group with 1 to 5 carbon atoms, and the three R1 groups may be identical or different, wherein prior to the polymerization or copolymerization, a methylpentene is pre-polymerized or pre-copolymerized in the presence of a catalyst comprising the catalyst component (A), a part of the catalyst component (B) and a part of the catalyst component (C) to form about 1 to about 1000 grams, per millimole of titanium atom, of a methylpentene polymer or copolymer.
A process for producing a polymer or copolymer of 4-methyl-1-pentene, which comprises polymerizing 4-methyl-1-pentene or copolymerizing 4-methyl-1-pentene with up to about 20 mole % of an olefin having 2 to 20 carbon atoms in the presence of a catalyst comprising (A) a solid highly active titanium catalyst component composed of magnesium, titanium, halogen and a diester of a dicarboxylic acid, (B) an organoaluminum compound, and (C) an organosilicon compound represented by the following formula R13Si(OR2) wherein each of R1 and R2 represents a hydrocarbon group with 1 to 5 carbon atoms, and the three R1 groups may be identical or different, wherein prior to the polymerization or copolymerization, a methylpentene is pre-polymerized or pre-copolymerized in the presence of a catalyst comprising the catalyst component (A), a part of the catalyst component (B) and a part of the catalyst component (C) to form about 1 to about 1000 grams, per millimole of titanium atom, of a methylpentene polymer or copolymer.
Description
:il Z23i()~
This invention relates to an improved process for producing a polymer or copolymer of 4-methyl-1-pentene having improved stereoregularity and bulk density with improved catalytic actlvity by polymerizing 4-methyl-1-pentene or copolymerizing 4-methyl-1-pentene with up to about 20 mole % of an olefin having 2 to 20 carbon atoms.
More specifically, this invention pertains to an improved process for producing a polymer or copolymer of 4-methyl-1-pentene,which comprises polymerizing 4-methyl-l-pentene or copolyrnerizing 4-methyl-1-pentene with up to about 20 mole% of an olefin having 2 to 20 carbon atoms (an olefin other than 4-methyl-1-pentene) in the presence of a catalyst comprising ~A) a solid highly acti~e titanium catalyst component composed of magnesium, titanium, halogen and a diester of a dicarboxylic acid, (B) an organoaluminum compound, and (C) an organosilicon compound represented by the following formula R13Si ( oR2 ) wherein each of Rl and R2 represents a hydrocarbon group with 1 to 5 carbon atoms, and the three ~1 groups may be identical or different, wherein prior to the polymerization or copolymerization, a methylpentene is pre-polymerized or pre-copolymerized in the presence of a catalyst comprising the catalyst component (A), a part of the catalyst component (B) and a part of the catalyst component (C) to form about 1 to about 1000 grams, per millimole of titanium atom, of a m~thylpentene polymer or copolymer.
A catalyst comprising (1) a solid highly active titanium catalyst component composed of magnesium, : ' ~,~5, : ~ `
.. :, , .. .,., ~ , . . :
3~
titanium, halogen and an electron donor, (2) an organo-aluminum compound and (3) optionally a third component such as a carboxylic acid ester or an organosilicon compound has previously been known -to he useful for the production of stereoregular polymers of co-polymers of alpha-o:Lefins having a~ l.east 3 carbon atoms, and many proposals have been made on this type of catalyst in the past. In particular, much work has been done on this type of catalysts suitabl~ fox the producti.on of stereoregular propylene polymer or copolymers. A number of improvements have been proposed on cata-lysts which can give highly stereoregular polypropylene in high yields.
When catalysts suitable for the polymerization of propylene are applied to the polymerization of 4-methyl-1-pentene, they show a fairly hi~h level of performance but do not prove to be entirely satisfactory in regard to the yield of the 4-methyl-1-pentene polymer per unit weight of the catalyst or the proportion of a stereoregular 4-methyl-1-pentene polymer in the resulting polymerization product.
For example, Japanese Laid-Open Patent Publication No. 63310/19~2 (published April 16, 1982, corresponding to Euro-pean Patent Application No. 45,977, published February 17, 1982) discloses a catalyst for polymerization of olefins which can ~enerally encompass a catalyst composed oF (a) an aluminum alkyl compound (b) a silicon compound containing at least one bond selected from the group consisting of an Si-oR bond, an Si-OCOR
bond and an Si-NR~ bond wherein R represents a hydrocarbonyl group, and (c) a solid highly active titanium catalyst component : ' ~ '. ' ,': ' ' ',' - ~, 1. . .: . , . '' `;' "~"' ' ' " . ,' :
'" '"' " ~ :' ' ' ": ' ' '''' ':
~, ,: ' .:
3~L()(~
- 2a -composed of magnesium, titanium, halogen and a diester.
This patent documen-t illustrates propylene, butene-l, styrene and 4-methylpentene as examples of the alpha-olefin to be polymerized, but all of the working exa~ples in this patent docu-ment are directed to the polymerization of propylene. No specific .: - . ........ . ,: ., ;
~ ., ,~,, ~ . ,:
' ~3~
working example is given about the polymerizatiorl of 4-rnethyl-1-pentene. This patent document describes as the silicon compound (b) compouncls of the f`ormula RmSiYnXp where:in R represents a Cl-C20 alkyl, alkenyl, aryl, arylalkyl or cycloalkyl group, Y represen-ts -OR', OOCOR' or -NR2' in which R' is identical to or different from R and has the same meaning as R, X represents a halogen or hydrogen atom, the group -OCOR" or the group -NR2" in which R" is identical to or different from R' and has the sarne meaning as R', m is a number of from O
-to 3, n is a number of from 1 to 4 and p is a number of from O to 1, provided that the sum of m, n and p is 4.
It, however, fails to show a compound of the above formula wherein m=3, n=l, p=O and Y is -OR', which compound can be included within the formula R13Si(OR2) representing the catalyst component (C) in the present invention. Naturally, it fails to show any working example in which such a compound falling within the formula of component (C) in this invention was used.
The present inventors have made investigations in order to develop a process for polyrnerizing or copolymerizing alpha--olefins having at least 3 carbon atoms, especially 4-methyl-1-pentene to give a highly stereoregular polymer or copolymer of such an olefin with a high catalytic efficiency. These investi~ations have led to the discovery that to achieve an improvement on the polymerization or copolymerization of 4-methyl-1-pentene, it is important to meet a combination o~ two parameters, i.e. the selection of a catalyst system composed of specific components and the pre-polymerization or pre-copolymerization of a methylpentene.
Investigations of the present inven-tors have shown that a polymer or copolymer of 4-methyl-1-pentene having improved stereoregularity and bulk density can be produced advantageously on an industrial scale with improved catalytic activity by polymerizing 4-methyl-1-pentene or copolymerizing 4-methyl-1-pentene with up to ... .
.
., .::
:... . :
~ ::. . -::
~2~3~
about 20 mole% of an olefin havi.ng 2 to 20 carbon atoms under a combination of the following two parameters, namely I. the use of a catalyst comprising (A) a solid highly acti.ve titanium catalyst component composed of magnesium, titanium, halogen and a diester of a dicarboxylic acid, (B) an organoaluminum compound, and (C) an organosilicon compound represented by the following formula R13Si(OR ) wherein each of Rl and R2 represents a hydro-carbon group having 1 to 5 carbon atoms and the three Rl groups may be identical or different; and II. prior to the polymerization or copolymeriza-tion, a methylpentene is pre-polymerized or pre-copolymerized in the presence of a catalyst comprising the catalyst component (A), a part of the catalyst component (B) and a part of the catalsyt component (C) to f~rm about 1 to about 1000 grams, per millimole of titanium atom, of a methylpentene polymer or copolymer.
The investigations of the present inventors have also shown that in performing the aforesaid pre-polymerization or pre-copolymerization, the organo-aluminum compound (B) and the organosilicon compound (C) can be used only partially, and the remainder of these components may be added to the reaction system at the time of polymerization or copolymerization.
It is an ob~ect of this invention to provide an improved process for producing a polymer or copolymer of 4-methyl-1-pentene.
The above and other objects and advantages of this invention will become more apparent from t~le . ~. ..
1~3~0 following description.
In the following descirption, the term polymerization is sometimes used -to mean both homo-polymeriæation and copolymerization, and the terrn polymer, to mean both a homopolymer and a copolymer.
The solid highly active titanium catalyst component (A) that can be used in this invention contains magnesium, titanium, halogen and a diester of a dicarboxylic acid as essential components.
The titanium catalyst component (A) desirably has a magnesium/titanlum atomic ratio of from about 2 to about 100, preferably from about 4 to about 70, a halogen/titanium atomic ratio of from about 4 to about 100, preferably from about 6 to about 40, and a diester/titanium mole ratio of from about 0.2 to about 10, preferably from about 0.4 to about ~. The specific surface area of the titanium catalyst component (A) is preferably at least about 3 m /g, more preferably at least about 40 m /g, especially preferably about 100 m /g, to about 800 m /g.
Usually, the titanium catalyst component (A) does not substantially liberate a titanium compound when treated by a simple means such as washing with hexane at room temperature.
The X ray spectrum of the titanium catalyst component (A) shows that irrespective of the starting magnesium compound used for its preparation, it shows an amorphous nature with regard to the magnesium compound or it is much more arnorphous than a usual commercially available magnesium dihalide.
In addition to the aforesaid essential components, the titanium catalyst component (A) may further include other elements, metals, functional groups, electron donors, etc. to an extent that they do not adversly affect the performance of the catalyst.
Or the component (A) rnay be diluted with an organic or inorganic diluent.
.:.
:~ .
:
'' :: ` ' ', : . ~
... . . .
.
::
~-3~0 Preferably, the titanium catalyst component (A) has an average particle diameter of about 1 to about 200 rnicrons, more preferably about 5 to about 100 microns, and the geometric deviation of its particle size distribution ~g, is preferably less than 2.1, more preferably not more than 1.95.
Preferably, the titanium catalyst component (A) has such a shape as a true spherical shape, an elliptical shape or a granular shape, and the shape is uniform.
The titanium catalyst component (A) may be prepared by contacting a magnesium compound (or metallic magnesium), a titanium cornpound and a diester or a compound capable of forming a diester with one another with or without using another reagent in accordance with the same metho.d of preparing known highly .
active titanium catalyst compon.ants, which are disclosed, for example, in British Patent Specifications Nos. 1492618, 1554340 and 1554248, U. S. Patents Nos.
20 4157435, 4076924, 4085276, 4250285, 4232139, 4143223, 4315874, 4330649, 4401589 and 4335015, and European Yatent Specification No. 22675.
Some examples of the procedure of producing the titanium catalyst component (A) are sumarized below.
(1) A magnesium compound or a complex of a magnesium compound and an electron donor is pre-treated or not-pretreated with an electron donor and/or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound in the presence or absence of an electron donor or a pulverization aid with or without pulverization. The resulting solid is reacted with a titanium compound which is in the liquid state under the reaction conditions. In the above `:
procedure, a diester of a dicarboxylic acid or a compound capable of forming the diester is used at least once as the electron donor.
This invention relates to an improved process for producing a polymer or copolymer of 4-methyl-1-pentene having improved stereoregularity and bulk density with improved catalytic actlvity by polymerizing 4-methyl-1-pentene or copolymerizing 4-methyl-1-pentene with up to about 20 mole % of an olefin having 2 to 20 carbon atoms.
More specifically, this invention pertains to an improved process for producing a polymer or copolymer of 4-methyl-1-pentene,which comprises polymerizing 4-methyl-l-pentene or copolyrnerizing 4-methyl-1-pentene with up to about 20 mole% of an olefin having 2 to 20 carbon atoms (an olefin other than 4-methyl-1-pentene) in the presence of a catalyst comprising ~A) a solid highly acti~e titanium catalyst component composed of magnesium, titanium, halogen and a diester of a dicarboxylic acid, (B) an organoaluminum compound, and (C) an organosilicon compound represented by the following formula R13Si ( oR2 ) wherein each of Rl and R2 represents a hydrocarbon group with 1 to 5 carbon atoms, and the three ~1 groups may be identical or different, wherein prior to the polymerization or copolymerization, a methylpentene is pre-polymerized or pre-copolymerized in the presence of a catalyst comprising the catalyst component (A), a part of the catalyst component (B) and a part of the catalyst component (C) to form about 1 to about 1000 grams, per millimole of titanium atom, of a m~thylpentene polymer or copolymer.
A catalyst comprising (1) a solid highly active titanium catalyst component composed of magnesium, : ' ~,~5, : ~ `
.. :, , .. .,., ~ , . . :
3~
titanium, halogen and an electron donor, (2) an organo-aluminum compound and (3) optionally a third component such as a carboxylic acid ester or an organosilicon compound has previously been known -to he useful for the production of stereoregular polymers of co-polymers of alpha-o:Lefins having a~ l.east 3 carbon atoms, and many proposals have been made on this type of catalyst in the past. In particular, much work has been done on this type of catalysts suitabl~ fox the producti.on of stereoregular propylene polymer or copolymers. A number of improvements have been proposed on cata-lysts which can give highly stereoregular polypropylene in high yields.
When catalysts suitable for the polymerization of propylene are applied to the polymerization of 4-methyl-1-pentene, they show a fairly hi~h level of performance but do not prove to be entirely satisfactory in regard to the yield of the 4-methyl-1-pentene polymer per unit weight of the catalyst or the proportion of a stereoregular 4-methyl-1-pentene polymer in the resulting polymerization product.
For example, Japanese Laid-Open Patent Publication No. 63310/19~2 (published April 16, 1982, corresponding to Euro-pean Patent Application No. 45,977, published February 17, 1982) discloses a catalyst for polymerization of olefins which can ~enerally encompass a catalyst composed oF (a) an aluminum alkyl compound (b) a silicon compound containing at least one bond selected from the group consisting of an Si-oR bond, an Si-OCOR
bond and an Si-NR~ bond wherein R represents a hydrocarbonyl group, and (c) a solid highly active titanium catalyst component : ' ~ '. ' ,': ' ' ',' - ~, 1. . .: . , . '' `;' "~"' ' ' " . ,' :
'" '"' " ~ :' ' ' ": ' ' '''' ':
~, ,: ' .:
3~L()(~
- 2a -composed of magnesium, titanium, halogen and a diester.
This patent documen-t illustrates propylene, butene-l, styrene and 4-methylpentene as examples of the alpha-olefin to be polymerized, but all of the working exa~ples in this patent docu-ment are directed to the polymerization of propylene. No specific .: - . ........ . ,: ., ;
~ ., ,~,, ~ . ,:
' ~3~
working example is given about the polymerizatiorl of 4-rnethyl-1-pentene. This patent document describes as the silicon compound (b) compouncls of the f`ormula RmSiYnXp where:in R represents a Cl-C20 alkyl, alkenyl, aryl, arylalkyl or cycloalkyl group, Y represen-ts -OR', OOCOR' or -NR2' in which R' is identical to or different from R and has the same meaning as R, X represents a halogen or hydrogen atom, the group -OCOR" or the group -NR2" in which R" is identical to or different from R' and has the sarne meaning as R', m is a number of from O
-to 3, n is a number of from 1 to 4 and p is a number of from O to 1, provided that the sum of m, n and p is 4.
It, however, fails to show a compound of the above formula wherein m=3, n=l, p=O and Y is -OR', which compound can be included within the formula R13Si(OR2) representing the catalyst component (C) in the present invention. Naturally, it fails to show any working example in which such a compound falling within the formula of component (C) in this invention was used.
The present inventors have made investigations in order to develop a process for polyrnerizing or copolymerizing alpha--olefins having at least 3 carbon atoms, especially 4-methyl-1-pentene to give a highly stereoregular polymer or copolymer of such an olefin with a high catalytic efficiency. These investi~ations have led to the discovery that to achieve an improvement on the polymerization or copolymerization of 4-methyl-1-pentene, it is important to meet a combination o~ two parameters, i.e. the selection of a catalyst system composed of specific components and the pre-polymerization or pre-copolymerization of a methylpentene.
Investigations of the present inven-tors have shown that a polymer or copolymer of 4-methyl-1-pentene having improved stereoregularity and bulk density can be produced advantageously on an industrial scale with improved catalytic activity by polymerizing 4-methyl-1-pentene or copolymerizing 4-methyl-1-pentene with up to ... .
.
., .::
:... . :
~ ::. . -::
~2~3~
about 20 mole% of an olefin havi.ng 2 to 20 carbon atoms under a combination of the following two parameters, namely I. the use of a catalyst comprising (A) a solid highly acti.ve titanium catalyst component composed of magnesium, titanium, halogen and a diester of a dicarboxylic acid, (B) an organoaluminum compound, and (C) an organosilicon compound represented by the following formula R13Si(OR ) wherein each of Rl and R2 represents a hydro-carbon group having 1 to 5 carbon atoms and the three Rl groups may be identical or different; and II. prior to the polymerization or copolymeriza-tion, a methylpentene is pre-polymerized or pre-copolymerized in the presence of a catalyst comprising the catalyst component (A), a part of the catalyst component (B) and a part of the catalsyt component (C) to f~rm about 1 to about 1000 grams, per millimole of titanium atom, of a methylpentene polymer or copolymer.
The investigations of the present inventors have also shown that in performing the aforesaid pre-polymerization or pre-copolymerization, the organo-aluminum compound (B) and the organosilicon compound (C) can be used only partially, and the remainder of these components may be added to the reaction system at the time of polymerization or copolymerization.
It is an ob~ect of this invention to provide an improved process for producing a polymer or copolymer of 4-methyl-1-pentene.
The above and other objects and advantages of this invention will become more apparent from t~le . ~. ..
1~3~0 following description.
In the following descirption, the term polymerization is sometimes used -to mean both homo-polymeriæation and copolymerization, and the terrn polymer, to mean both a homopolymer and a copolymer.
The solid highly active titanium catalyst component (A) that can be used in this invention contains magnesium, titanium, halogen and a diester of a dicarboxylic acid as essential components.
The titanium catalyst component (A) desirably has a magnesium/titanlum atomic ratio of from about 2 to about 100, preferably from about 4 to about 70, a halogen/titanium atomic ratio of from about 4 to about 100, preferably from about 6 to about 40, and a diester/titanium mole ratio of from about 0.2 to about 10, preferably from about 0.4 to about ~. The specific surface area of the titanium catalyst component (A) is preferably at least about 3 m /g, more preferably at least about 40 m /g, especially preferably about 100 m /g, to about 800 m /g.
Usually, the titanium catalyst component (A) does not substantially liberate a titanium compound when treated by a simple means such as washing with hexane at room temperature.
The X ray spectrum of the titanium catalyst component (A) shows that irrespective of the starting magnesium compound used for its preparation, it shows an amorphous nature with regard to the magnesium compound or it is much more arnorphous than a usual commercially available magnesium dihalide.
In addition to the aforesaid essential components, the titanium catalyst component (A) may further include other elements, metals, functional groups, electron donors, etc. to an extent that they do not adversly affect the performance of the catalyst.
Or the component (A) rnay be diluted with an organic or inorganic diluent.
.:.
:~ .
:
'' :: ` ' ', : . ~
... . . .
.
::
~-3~0 Preferably, the titanium catalyst component (A) has an average particle diameter of about 1 to about 200 rnicrons, more preferably about 5 to about 100 microns, and the geometric deviation of its particle size distribution ~g, is preferably less than 2.1, more preferably not more than 1.95.
Preferably, the titanium catalyst component (A) has such a shape as a true spherical shape, an elliptical shape or a granular shape, and the shape is uniform.
The titanium catalyst component (A) may be prepared by contacting a magnesium compound (or metallic magnesium), a titanium cornpound and a diester or a compound capable of forming a diester with one another with or without using another reagent in accordance with the same metho.d of preparing known highly .
active titanium catalyst compon.ants, which are disclosed, for example, in British Patent Specifications Nos. 1492618, 1554340 and 1554248, U. S. Patents Nos.
20 4157435, 4076924, 4085276, 4250285, 4232139, 4143223, 4315874, 4330649, 4401589 and 4335015, and European Yatent Specification No. 22675.
Some examples of the procedure of producing the titanium catalyst component (A) are sumarized below.
(1) A magnesium compound or a complex of a magnesium compound and an electron donor is pre-treated or not-pretreated with an electron donor and/or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound in the presence or absence of an electron donor or a pulverization aid with or without pulverization. The resulting solid is reacted with a titanium compound which is in the liquid state under the reaction conditions. In the above `:
procedure, a diester of a dicarboxylic acid or a compound capable of forming the diester is used at least once as the electron donor.
(2) A magnesium compound in the liquid state .. .
., ,.
; .
..
. ;: .
. ~ .
: LZ2310~
having no reducing ability is reacted with a titanium compound in the liquid state in the presence of a diester of a dicarboxylic acid or a compound capable of formin~ the diester to precipitate a solid titanium complex.
., ,.
; .
..
. ;: .
. ~ .
: LZ2310~
having no reducing ability is reacted with a titanium compound in the liquid state in the presence of a diester of a dicarboxylic acid or a compound capable of formin~ the diester to precipitate a solid titanium complex.
(3) The product obtained in (2) above is further reacted with a titanium compound.
(4) The product obtained in (l) or (2) is further reacted with a titanium compound and as an electron donor, a diester of a dicarboxylic acid or a compound capable of forming the diester.
(5) A magnesium compound or a complex of a rnagnesium compound and an electron donor is pulverized in the presence of a titanium compound and in the presence or absence of an electron donor and a pulverization aid, and with or without pre-treatment with an electron donor and/or a reaction aid such as an organo-aluminum compound or a halogen-containing silicon compound, treated with a halogen, a halogen compound or an aromatic hydrocarbon. In the above procedure, a diester of a dicarboxylic acid or a compound capable of forming the diester is used at least once as the electron donor.
Preferred among these methods are those in which a liquid titanium halide is used, or a halogenated hydrocarbon is used after or during the use of the titanium compound.
The electron donor used in the above methods of preparation is not necessarily limited to the diester or diester-~orming compound. There may be used other electron donors such as alcohols, phenols, aldehydes, ketones, ethers, carboxylic acids, carboxylic acid anhydrides, carbonic acid esters, monoesters and amines. It is essential however that the diester of a dicarboxylic acid or the diester-forming Compound be used at least once.
Preferred examples of the diester as an ,:, - .
.:- . -, . - .- ~
. .:- - :,:
. -.. . ~ ;; ;
.. ~
1~23~
essential componen~ of the solid hi.ghly active titanium cata].yst component (A) used in thi.s invention include diesters o~ dicarboxylic acids in which two carboxyl groups are attached to one carbon atorn of the hydrocarbon moiety or dicarboxylic acids in which one carboxyl group is attached to each of the two adjoining carbon atoms of the hydrocarbon moiety, and diesters of dicarboxylic acids in which one carboxyl group is attached to each o~ the two adjoining carbon atoms of the heterocyclic compound moiety containing at least two carbon atoms.
More specific examples of the preferred diesters are diesters, preferably di(Cl-C20)alkyl esters in which the two alkyl groups may be identical or different, of dicarboxylic acids in which two carboxyl groups are attached to one carbon atom of an aliphatic hydrocarbon moiety having l to 20 carbon atoms or dicarboxylic acids in which one carboxyl group is attached to each of the two adjoining carbon atoms of an aliphatic hydrocarbon moiety having 2 to 20 carbon atoms; diesters, preferably di(C1-C20)alkyl esters in which the two alkyl esters may be identical or different, o~ dicarboxylic acids in which two carboxyl groups are attached to bne carbon atom of an alicyclic hydrocarbon 2S moiety having 3 to 20 carbon atoms or dicarboxylic acids in which one carboxyl group is attached to each of the two adjoining carbon atoms of the aforesaid alicyclic hydrocarbon moiety; diesters, preferably di(Cl-C20)alkyl esters in which the two alkyl groups may be identical or different, of dicarboxylic acids in which one carboxyl group is attached to each of the adjoining carbon atoms (at the ortho-position) of an aromatic hydrocarbon moiety having 6 to 20 carbon atoms; and diesters, preferably di(Cl-C20)alkyl esters, of dicarboxylic acids in which one carboxyl group is attached to each of the two adjoining carbon atoms of a heterocyclic compound moiety containing at least two ., ,.
~3~
g carbon atoms and 1 to 10 hetero atoms selected from the group conslsting of 0, N and S atoms.
Specific examples of the dicarboxylic acids exemplified above include malonic acid; substituted malonic acids such as methylrnalonic acid, ethylmalonic acid, isopropylmalonic acid, allylmalonic acid, and phenylmalonic acid; succinic acid; substituted succinic acids such as methylsuccinic acid, dirnethylsuccinic acid, ethylsuccinic acid, methylethylsuccinic acid and itaconic acid; maleic acid; substituted maleic acids such as citraconic acid and dimethylmaleic acid, fumaric acid; substituted fumaric acid such as methylfumaric acid and ethylf~maric acid alicyclic dicarboxylic acids such as cyclopentane-l,l-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclchexene-1,2-dicarboxylic acid, cyclohexene-2,3-dicarboxylic acid cyclohexene-3,4-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, Nadic Acid, Methylnadic ACid, and 1-allylcyclohexane-3,~-dicarboxylic acid;
aromatic dicarboxylic acids such as phthalic acid, naphthalene 1,2-dicarboxylic acid and naphthalene-2,3-- dicarboxylic acid; and heterocyclic dicarboxylic acids such as furane-3,4-dicarboxylic acid, 4,5-dihydrofurane-2,3-dicarboxylic acid, benzopyran-3,4-dicarboxylic acid, pyrrole-2,3-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, and indole-2,3-dicarboxylic acid.
Preferably, at least one of the alcohol components of the dicarboxylic acid diesters exemplified above has at least 2 carbon atoms, for example 2 to 20 carbon atoms, especially at least 3 carbon atoms. It is above all preferred that both of the alcohol components have at least 2 carbon atoms, especially at least 3 carbon atoms. Examples include the diethyl esters, diisopropyl esters, di-n-propyl esters, di-n-butyl esters, diisobutyl esters, di-tert-butyl esters, diisoamyl esters, di-n-hexyl esters, di-2-ethylhexyl esters, di-n-octyl esters, diisodecyl esters, ar~d ethyl-.::
. - ' ' :lZ23~
n-butyl esters of the above-exemplified dicarboxylic acids.
Both a magnesium compound having reducing ability and a magnesium compound having no reducing ability can be utilized in the preparation of the solid highly active titaniurn catalyst component (A).
The former includes, ~or example, magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, for example di(Cl-C20 alkyl) magnesiums such as dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, ethylbutyl magnesium, diamyl magnesium, dihexyl magnesium and didecyl magnesium;
Cl-C20 alkylmagnesium chlorides such as ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride and amylmagnesium chloride; Cl-C2~ alkyl-C1-C20 alkoxymagnesiums such as butylethoxy magnesium; and Cl-C20 alkylmagnesium hydrides such as butylmagnesium hydride. These magnesium compounds may be used in the form of a complex with an organoaluminum compound, for example, or may be in the ~orm o~ a liquid or a solid.
The latter includes, for example, magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium ~luoride; Cl-C20 alkoxy-magnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride and octoxymagnesium chloride;
C~-C20 aryloxymagnesium halides such as phenoxy magnesium chloride and methylphenoxymagnesium chloride; Cl-C20 alkoxymagnesiums such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, and 2-ethylhexoxy magnesium, C6-C20 aryloxy magnesiums such as phenoxy magnesium and dime-thylphenoxy magnesium; and carboxylic acid salts o~ magnesium such as Magnesium laurate and magnesium stearate. These magnesium compounds having no reducing ability may be derived from the a~ore-said magnesium compounds having reducing ability, or those derived during the preparation o~ the catalyst component.
The above magnesium compounds may be a complex with other ,, '' ' ' ~Z~3~
metals or mixtures of other metal compounds. Or they may be A rnixture of two or more of these compounds.
Preferred are the magnesium compounds having no reducing ability, and halogen~containing magresium compounds, particularly, magnesium chloride, alkoxy magnesium chlorides and aryloxymagnesium chlorides are preferred.
Suitable titanium compounds used to prepare the titanium catalyst component (A) are tetravalent titanium compounds represented by Ti(OR)gX4 g in which R is a hydrocarbon group, X is halogen and g is O to 4.
Examples of R are alkyl groups having 1 to 6 carbon atoms. Examples of X are Cl, Br and I.
Specific examples of such titanium compounds include titanium tetrahalides such as TiC14, TiBr4 and TiI4; alkoxytitanium trihalides such as Ti(OCH3)C13, Ti(OC2H5)C13, Ti(O n-C4Hg)C13, Ti(OC2H5)Br3 and Ti(O iso-C4~9)Br3; alkoxytitanium dihalides such as Ti(OCH3)2C12, Ti(OC2H5)2C12, Ti~O n-C4Hg)2Cl2 and Ti(OC2H5)2Br2; trialkoxytitanium monohalides such as Ti(OCH3)3Cl, Ti(OC2H5)3C1, Ti(O n-C4Hg)3Cl and Ti(OC2H5)3Br; and tetraalkoxytitaniums such as Ti(OCH3)4, Ti(OC2H5)4 and Ti(O n-C4Hg)4. Among them, the halogen-containing titanium compounds, particularly titanium tetrahalides, especially preferably titanium tetrachloride, are preferred. These titanium compounds may be used singly or as a mixture. Or they may be used as diluted in hydrocarbons or halogenated hydrocarbons.
In the preparation o~ the titanium catalyst component (A), the arnounts of the titanium compound, the magnesium compound the electron donor to be supported, and the other electron donors such as alcohols, phenols, rnonocarboxylic acid esters, the silicon compound and the aluminum compound which may used as required differ depending upon the method of preparation and cannot be defined in a general manner. For example, about 0.1 to ~ - ;
, ' ' , ' ~ : ' "'',':'`
12;~3~)0 about 10 moles of the electron donor to be supported and about 0.05 mole to about 1000 moles of the titanium compound may be used per mole of the magnesium compound.
In the present invention, a catalyst composed of the solid highly active titanium catalyst component composed of magnesium, titanium, halogen and a diester of a dicarboxylic acid prepared as above, (B) an organoaluminum compound and (C) an organosilicon compound of the formula R 3Si(OR ) is used.
Examples of the organoaluminum compound (B) include (i) organoaluminum compounds at least having an Al-carbon bond in the molecule, for example organoaluminum compounds r.epresented by the general formula R3mAl(OR4)nHpXq wherein each of R3 and R represents a hydrocarbon, for example a Cl-C15 hydrocarbon group, preferably Cl-C4 hydrocarbon group, X represents a halogen atom such as Cl, Br or I, O~m-3, O~n~3, 0-~p~3~ 0-q<3, provided that m+n+p~q=3, and (ii) complex alkylated products of aluminum and a metal of Group I of the periodic table represented by the following general formula MlAlR34 wherein ~1 is Li, Na or K, and R3 is as defined above.
Examples of the hydrocarbon groups for R3 and R4 are alkyl groups.
Examples of the organoaluminum compounds (i) are those of the general formulae R3 Al(OR4)3_m wherein R3 and R4 are as defined above, and m is preferably a number represented by ,:,^
. ` '' . .~
.
1`
lZ;~33l~
1.5-m-3, R mAlX3 m wherein R and x are as defined above, and m is preferably a number represented by O<m<3, R3mAlH3_m wherein R3 is as defined above, and m is preferably a number represented by 2-m<3, and R3mAl(oR4)nXq wherein R3 and R4 are as defined above, X is the same halogen as above, O<m-3, 0-n~3, O-q~3, m+n~q=3, Examples of the organoaluminum compounds (i) include trialkyl aluminums such as triethyl aluminum and tributyl aluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkyl aluminum alkoxides such as .
diethyl aluminum ethoxide and dibutyl aluminum butoxide;
partially alkoxylated alkyl aluminums such as alkyl aluminum sesquialkoxides (e.g., ethyl aluminum 2G sesquiethoxide and butylaluminum sesquibutoxide) and partially alkoxylated alkyl aluminums having the average composition represented by R2 5Al~OR2)o 5; dialkyl : aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide;
alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; partially halogenated alkyl aluminums9 ~or example alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; other partially hydrogenated alkyl aluminums, for example alkyl aluminum dihydrides . .~
,., ~ .: ..
~3~
such as ethyl aluminum dihydride and propyl aluminum dihydride; and partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxychloride, ethyl aluminum butoxy chloride and ethyl aluminl~m ethoxy bromide.
LiAl(C2H5)4 and LiAl(C7H15)4 may be cited as examples of the compounds (ii).
There may also be used organic aluminum compounds in which two or more aluminum atoms are bonded through an oxygen or nitrogen atom, which are similar to the compounds (i). Examples are (C2H5)2AlOAl(C2H5)2, (C4Hg)2AlOAl(C4H9)2, and (C2H5)2AlNAl(C2H5)2.
Of these, the trialkyl aluminums and ths alkyl aluminums in which two or more aluminum atoms are bonded are preferred.
The organosilicon compound (C) constituting the catalyst of this invention together with the components (A) and (~) described above is represented by the ~ollowing formula R 3Si(OR ).
In the formula, Rl and R each represent a hydrocarbon group having 1 to 5 carbon atoms, and the three ~1 groups may be identical or different.
Examples of the hydrocarbon group for Rl and R are alkyl, alkenyl, cycloalkyl, haloalkyl and alkoxyalkyl groups having 1 to 5 carbon atoms. Specific examples of the organosilicon compound (C) are trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propoxysilane, triethylmethoxysilane 9 tri-n-propylmethoxysilane, tri-iso-propylmethoxysilane tri-n-butylmethoxysilane, tri iso-butylmethoxysilane, tri-n-amylmethoxysilane and tri-iso-amylmethoxysilane.
In the present invention, 4-methyl-1-pentene is polymerized in the presence o~ the catalyst composed , -~ .
~2~23~
of the components (A), (B) and (C) described above.
Prior to the polymerization, a methylpentene is pre-polymerized in a hydrocarbon medium in the presence of the component (A), a part of the component (B) and a part of the component (C) to form about 1 to about 1000 g, per millimole of titanium in the component (A), of a polymer of the methylpentene. By performing the pre-polymerization, a powdery polymer having a high bulk density can be obtained in the subsequent slurry polymerization of 4-methyl~l-pentene. Accordingly, this offers the advantage that the performance of the slurry is good and the operation can be carried out at high polymer concentrations. Another advantage is that the amount of the polymer yielded per unit amount of the catalsyt is large, and a stereoregular polymer can be produced in a high proportion.
The methylpentene used in the pre-polymeriza-tion can be selected from 3-methyl-1-pentene, ~-methyl-l-pentene, 4,4-dimethyl-1-pentene, etc. Preferably, the pre-polymerization is carried out under relatively mild conditions and under such conditions that the pre-polymer obtained does not dissolve in the polymerization medium. For this purpose, the polymerization medium is preferably an inert hydrocarbon, for example an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, and an alicyclic hydrocarbon such as cyclopentane and cyclohexane.
In the pre-polymerization, it is preferred to use the titanium catalyst component (A) in an amount, calculated as titanium atom, of about 0.5 to aobut 1000 millimoles, particularly about 1 to about 10 millimoles per liter of the hydrocarbon medium. The organoaluminum compoudn (B) is used preferably in an Al/Ti atomic ratio of from about 1 to about 100, particularly from about 2 to about 20, and the organo-silicon compound ~C) is used preferably in an amount of .
, ~
:. . :
-, .
.... .... , :
3~
about 0.01 to about 2 moles, particularly about 0.02 to about l mole, per mole of the component (B).
I'he arnount of the methylpentene pre-polymerized is in the range of about l to about lO00 g, preferably about 3 to about lO0 g, per mi.llimole of the titanium in the component (~). The concentration of the methyl-pentene in the pre-polymerization is preferably not more than about l mole, especially not more than about 0.5 mole, per liter of the hydrocarbon medium.
Desirably, the pre-polymerization is carried out at a temperature at which the resulting pre-polymer does not dissolve in the hydrocarbon medium. The temperature varies depending upon the kind of the hydrocarbon medium, but is, for example, about -20C
to about -~70C, preferably about 0C to about 50C.
The pre-polymerization pressure may, for example, be atmospheric pressure to about lO kg/cm .
In the process of this invention, 4-methyl-l-pentene is polymerized or copolymerized by usin~ the catalyst subjected to the pre-polymerization treatment.
At this time, additional amounts o.f the component (B) and/or the component (C) may be supplied. Preferably, the component (B) i5 additionally used in an amount o~
about l to aobut lO00 moles, especially about lO to about 500 moles, per mole of the titanium and the component (C), in an amount of about 0.005 to about 2 moles, particularly about 0.01 to about l mole, per mole of the component (B).
When 4-methyl-l-pentene is to be copolymerized, ethylene and/or another alpha-olefin may be properly chosen. The comonomer may, for example, be an olefin having 2 to 20 carbon atoms other than 4-methyl-l-pentene such as ethylene, propylene, l-butene, l-pentene, l-pentene, l~hexene, 1-octene, l-decene, l-dodecene, l-tetradecene, l-octadecene and 3-methyl-l-pentene.
l`n the copolymerization, the proportion of the comonomer is desirably selected such ~hat the content of ..
12~ 0~
~ 17 -4-methyl-1-pen-~ene in the resulting copolymer becomes at least about 80 mole%, particularly at least about 90 mole %.
Polymerization of 4-methyl-1-pentene ls carried out preferably by the slurry polymerization techni-que. The polymerization medium may be 4-methyl-1-pentene itself, or an inert hydrocarbon such as those exemplified hereinabove for the pre-polymerization, The polymerization temperature maybe properly selected from those at which the slurry polymerization is possible. It varies depending upon the kind of the polymerization medium, but is preferably from about 20C to about 100C, preferably from about 30C to about 80C. It is preferred to employ a polymerization temperature higher (for example 9 at least about 5C
higher) than the temperature at which the prepolymeri-zation or pre-copolymerization is carried out. A
molecular weight controlling agent such as hydrogen may be used as required in order to control the molecular weight of the resulting polymer.
The polymerization pressure may, for example, be from atmospheric pressure to about 20 kg/cm2.
According to this invention, the yield of the polymer per unit amount of titanium is high, and the proportion of a stereoregular polymer formed is high.
In particularly, in the copolymerization of 4-methyl-1-pentene with ethylene and~or another alpha-olefin, the proportion of a solvent-soluble polymer formed is small, and the resulting copolymer shows a single melting point and has a narrow cornposition distribution.
The following Exarnples and Comparative Examples illustrate the present invention more specifically.
Example 1 Prep_ration of a titanium catalyst component (A) Anhydrous magnesium chloride (4~76 g; 50 mmoles), 25 ml of decane and 23.4 ml (150 mmoles) of 2-ethylhexyl alcohol were heated at 130C for 2 hours to .. : , :'~ ' ;~ ' :
.~:~ . ., :, "
i~Z3~
form a uniform solution. To the solution was added 1.11 g (7.5 rnmoles) of phthalic anhydride, and -the mixture was stirred at 130 C for 1 hour to dissolve phthalic anhydride in the uniform solution. The resulting uniform solution was cooled to room temperature, and added dropwise over 1 hour to 200 ml (1.8 moles) of titanium tetrachloride kept at -20C. After the addition, the mi~ture was heated to 110C over 4 hours.
When its temperature reached 110C, 2.68 ml (12.5 mmoles) of diisobutyl phthalate was added, and the mixture was maintained at this temperature for 2 hours with stirring. After the 2-hours reaction, the reaction mixture was hot-filtered to collect the solid portion.
The solid portion was again suspended in 200 ml of TiC14, and reacted again at 110C for 2 hours. After the reaction, the solid portion was collected again by hot filtration. It was fully washed with decane and hexane a-t 110C until no free titanium compound was detected from the washings. The titanium catlayst component (A) so prepared was stored as a hexane slurry.
A part of the component (A), however, was dried in order to examine its compoposition. It was found that the titanium catalyst component (A) contained 3.1% by weight of titanium9 56.0% by weight of chlorine, 17.0%
by weight of magnesium and 20.9% by weight of diiso-butyl phthalate.
Prepolymerization A 500 ml flask was charged with 200 ml of n-decane, 10 rnmoles of triethyl aluminum, 2 mmoles of trimethylmethoxysilane and 1 mmole, calculated as titanium atom, of the titanium catalyst component (A).
While maintaining a temperature of 25C, 30g of 4-methyl-l-pentene was added over the course of 60 minutes, and further reacted at 25C for 30 minutes. The reaction product was filtered by a glass filter, washed three times with 300 ml in total of n-decane, and again suspended in 200 ml of` n~decane. The amount of "` :
;:
~2;~3~
4-methyl-1-pentene pre-polymerized was 30 g per mmole of titanium.
P ymerization A l-liter au-toclave was charged with 500 ml of ~-methyl-l-pentene, C.5 mmole o~ triethyl aluminum, 0.05 mmole of trimethylmethoxysilane, 0.0025 mmole, calculated as titanium atom, of the pre-polymerization product, and 250 ml of hydrogen, and 4-methyl-1-pentene was polymerized at 50C for 30 minutes. Methanol was added to stop the polymerization. The polymerization product was filtered by a glass filter to separate it into a white powdery poly(4-methyl-1-pentene) and a sol~ent-soluble polymer.
The stereoregularity index (II) of the polymer was expressed as a percentage of a boiling n-heptane-insoluble portion based on the total amount of the polymer. The polymerization activity was expressed as grams of the entire polymer per mmole of titanium. The polymerization activity9 the II and the bulk density are shown in Table 1.
Comparative Example 1 4-Methyl-l-pentene was polymerized under the same conditions as in Example 1 except that the titanium catalyst component (A) was not subjected to the pre-polymerization treatment. The results are shown inTable 1. These results show the effects of the pre-polymerization.
Comparative Example 2 The same polymerization as in Example 1 was per~ormed except that diphenyldimethoxysilane capable of exhibiting high performance in the polymerization of propylene was used as the organosilicon compound. The results are shown in Table 1.
Comparative Example 3 The same polymerization as in Example 1 was carried out except that diphenyldimethoxysilane was used as the organic silicon compound in the pre-polymerization, . .
. , - ~, . -.. - .
- :
: : :
~2231~10 and trimethylmethoxysilane was used as the organosilicon compound in -the polymerization. The results are shown in Table 1.
Comparativ Example_4 The same polymerization as in Example 1 was carried out except that trimethylmethoxysilane was used as the organosilicon compound in the pre-polymerization, and diphenyldimethoxysilane was used as the organo-silicon compound in the polymerization. The results are shown in Table 1.
The results obtained in Gomparative Examples 3 and 4 show that the organosilicon compound of the ~ormula R13Si(OR2) is necessary both in the pre-polymeri-zation and the polymerization.
Examples 2 and 3 Example 1 was repeated except that the organosilicon compounds used in the polymerization and the prepolymerization were changed as shown in Table lo The results are also shown in Table 1.
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_ 21 rl ~) ~rl ~ l O r1 a) 0 0 O O
rl ~ E ~J 0 ~ ) 0 ~ ~
~, ::~ a) ~ o o o o o o o a)~ q~ ~_ E_ ____ __ __ . __ r OH _~ ~`U LO 1~
H ~ 0 (D rl ~ O ~ 0 S~_ a) co ~) .__ .__ .. _ _ 07h ~ rl O O O O O O O
~q) ~ ~rl O O O O O O O O
r~l E O :~ E O o ~ t` o ~ (o ~:~ r~ ~rl E-- ~ .. ..
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r-l ~1) r~l rf ~-1 ~ Q~ rl rl rl Q~ rl rl rl rl rl r l rl ~q O h rl rl rl rl ~ rl rl rl ~ rl h rl Q~ E~ Q U~
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E ~ Q o E~ X ~ X X X X ~ -E ~ ~ ~ X 1~ 1 ~ X X
X ~1 0 ~1 X t) [s~ L1 ._ __ _ _ I
.'.~ ' :'` : f .. , ~. , ~: :
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~Z3~3~t Example 4 A l-liter autoclave was charged with 500 ml of ~-methyl-l-pentene, 10 ml of l-decene, 0.5 mmoles of triethyl aluminum, 0.05 mmole o~ trimethylmethoxy-silane, 0.0025 mmole, calculated as titanium atom, ofthe pre-polymerization product as prepared in Example 1, and 250 ml o~ hydrogen, and the rnonomers were polymerized at 50C for 30 minutes. Methanol was added to stop the polymerization. The polymerization product was filtered by a glass filter to separate it into a white powdery 4-methyl-1-pentene/1-decene copolymer and a solvent-soluble polymer. The polymerization activity, the amount of the solvent-soluble polymer and the decene content, the melting point and bulk density of the powdery copolymer are shown in Table 2.
The melting point was measured as follows by using DSC. The sampel was heated from room temperature to 280C, and then cooled from 280C to -20C. After this preliminary treatment, the sample was again heated and its melting point was measured. The rate of temperature elevation and lowering was 10C/min.
Comp _ a-tive Example 5 The same polymerization as in Example 4 was carried out except that the titanium catalyst component prepared in Example 1 was used without the pre-polymeriza-tion. The results are shown in Table 2. The results show the effec-t of the prepolymerization.
Com~arative Example 6 Example 4 was repeated except that diphenyl-methoxysilane was used as the organosilicon compound in the pre-polymerization and the polymerization. The results are shown in Table 2. The results show the e~fect of using the specific organosilicon compound.
Examples 5 and 6 Example 4 was repeated except that l-hexene or l-octadecene was used as the comonomer. The results are shown in Table 2.
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Examples 7 to 9 Exarnple 4 was repeated except tha-t trimethyl--ethoxysilane, triethylrnethoxysilane or tri-n-propylmethoxysilane was used as the organosilicon S compound in the pre-polymerization and the polymerization.
The results are shown in Table 2.
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o x ta E~ O ~ ~0 0 0 ::~ C -- o o o o o o o o m ~ ~_ ~ ~ O h ~_ ~0 ~ ~ p ~ ~ ~ t O t\l CL) O
u~ O ~ 1 3 C\l ~D o c~
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a~ ~0 ~ ~ ~ X g ~ O
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~ ,1 ~ a ~ ~ ~_,I Q 1 O O ~ N S ~ C S S
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Preferred among these methods are those in which a liquid titanium halide is used, or a halogenated hydrocarbon is used after or during the use of the titanium compound.
The electron donor used in the above methods of preparation is not necessarily limited to the diester or diester-~orming compound. There may be used other electron donors such as alcohols, phenols, aldehydes, ketones, ethers, carboxylic acids, carboxylic acid anhydrides, carbonic acid esters, monoesters and amines. It is essential however that the diester of a dicarboxylic acid or the diester-forming Compound be used at least once.
Preferred examples of the diester as an ,:, - .
.:- . -, . - .- ~
. .:- - :,:
. -.. . ~ ;; ;
.. ~
1~23~
essential componen~ of the solid hi.ghly active titanium cata].yst component (A) used in thi.s invention include diesters o~ dicarboxylic acids in which two carboxyl groups are attached to one carbon atorn of the hydrocarbon moiety or dicarboxylic acids in which one carboxyl group is attached to each of the two adjoining carbon atoms of the hydrocarbon moiety, and diesters of dicarboxylic acids in which one carboxyl group is attached to each o~ the two adjoining carbon atoms of the heterocyclic compound moiety containing at least two carbon atoms.
More specific examples of the preferred diesters are diesters, preferably di(Cl-C20)alkyl esters in which the two alkyl groups may be identical or different, of dicarboxylic acids in which two carboxyl groups are attached to one carbon atom of an aliphatic hydrocarbon moiety having l to 20 carbon atoms or dicarboxylic acids in which one carboxyl group is attached to each of the two adjoining carbon atoms of an aliphatic hydrocarbon moiety having 2 to 20 carbon atoms; diesters, preferably di(C1-C20)alkyl esters in which the two alkyl esters may be identical or different, o~ dicarboxylic acids in which two carboxyl groups are attached to bne carbon atom of an alicyclic hydrocarbon 2S moiety having 3 to 20 carbon atoms or dicarboxylic acids in which one carboxyl group is attached to each of the two adjoining carbon atoms of the aforesaid alicyclic hydrocarbon moiety; diesters, preferably di(Cl-C20)alkyl esters in which the two alkyl groups may be identical or different, of dicarboxylic acids in which one carboxyl group is attached to each of the adjoining carbon atoms (at the ortho-position) of an aromatic hydrocarbon moiety having 6 to 20 carbon atoms; and diesters, preferably di(Cl-C20)alkyl esters, of dicarboxylic acids in which one carboxyl group is attached to each of the two adjoining carbon atoms of a heterocyclic compound moiety containing at least two ., ,.
~3~
g carbon atoms and 1 to 10 hetero atoms selected from the group conslsting of 0, N and S atoms.
Specific examples of the dicarboxylic acids exemplified above include malonic acid; substituted malonic acids such as methylrnalonic acid, ethylmalonic acid, isopropylmalonic acid, allylmalonic acid, and phenylmalonic acid; succinic acid; substituted succinic acids such as methylsuccinic acid, dirnethylsuccinic acid, ethylsuccinic acid, methylethylsuccinic acid and itaconic acid; maleic acid; substituted maleic acids such as citraconic acid and dimethylmaleic acid, fumaric acid; substituted fumaric acid such as methylfumaric acid and ethylf~maric acid alicyclic dicarboxylic acids such as cyclopentane-l,l-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclchexene-1,2-dicarboxylic acid, cyclohexene-2,3-dicarboxylic acid cyclohexene-3,4-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, Nadic Acid, Methylnadic ACid, and 1-allylcyclohexane-3,~-dicarboxylic acid;
aromatic dicarboxylic acids such as phthalic acid, naphthalene 1,2-dicarboxylic acid and naphthalene-2,3-- dicarboxylic acid; and heterocyclic dicarboxylic acids such as furane-3,4-dicarboxylic acid, 4,5-dihydrofurane-2,3-dicarboxylic acid, benzopyran-3,4-dicarboxylic acid, pyrrole-2,3-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, and indole-2,3-dicarboxylic acid.
Preferably, at least one of the alcohol components of the dicarboxylic acid diesters exemplified above has at least 2 carbon atoms, for example 2 to 20 carbon atoms, especially at least 3 carbon atoms. It is above all preferred that both of the alcohol components have at least 2 carbon atoms, especially at least 3 carbon atoms. Examples include the diethyl esters, diisopropyl esters, di-n-propyl esters, di-n-butyl esters, diisobutyl esters, di-tert-butyl esters, diisoamyl esters, di-n-hexyl esters, di-2-ethylhexyl esters, di-n-octyl esters, diisodecyl esters, ar~d ethyl-.::
. - ' ' :lZ23~
n-butyl esters of the above-exemplified dicarboxylic acids.
Both a magnesium compound having reducing ability and a magnesium compound having no reducing ability can be utilized in the preparation of the solid highly active titaniurn catalyst component (A).
The former includes, ~or example, magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, for example di(Cl-C20 alkyl) magnesiums such as dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, ethylbutyl magnesium, diamyl magnesium, dihexyl magnesium and didecyl magnesium;
Cl-C20 alkylmagnesium chlorides such as ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride and amylmagnesium chloride; Cl-C2~ alkyl-C1-C20 alkoxymagnesiums such as butylethoxy magnesium; and Cl-C20 alkylmagnesium hydrides such as butylmagnesium hydride. These magnesium compounds may be used in the form of a complex with an organoaluminum compound, for example, or may be in the ~orm o~ a liquid or a solid.
The latter includes, for example, magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium ~luoride; Cl-C20 alkoxy-magnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride and octoxymagnesium chloride;
C~-C20 aryloxymagnesium halides such as phenoxy magnesium chloride and methylphenoxymagnesium chloride; Cl-C20 alkoxymagnesiums such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, and 2-ethylhexoxy magnesium, C6-C20 aryloxy magnesiums such as phenoxy magnesium and dime-thylphenoxy magnesium; and carboxylic acid salts o~ magnesium such as Magnesium laurate and magnesium stearate. These magnesium compounds having no reducing ability may be derived from the a~ore-said magnesium compounds having reducing ability, or those derived during the preparation o~ the catalyst component.
The above magnesium compounds may be a complex with other ,, '' ' ' ~Z~3~
metals or mixtures of other metal compounds. Or they may be A rnixture of two or more of these compounds.
Preferred are the magnesium compounds having no reducing ability, and halogen~containing magresium compounds, particularly, magnesium chloride, alkoxy magnesium chlorides and aryloxymagnesium chlorides are preferred.
Suitable titanium compounds used to prepare the titanium catalyst component (A) are tetravalent titanium compounds represented by Ti(OR)gX4 g in which R is a hydrocarbon group, X is halogen and g is O to 4.
Examples of R are alkyl groups having 1 to 6 carbon atoms. Examples of X are Cl, Br and I.
Specific examples of such titanium compounds include titanium tetrahalides such as TiC14, TiBr4 and TiI4; alkoxytitanium trihalides such as Ti(OCH3)C13, Ti(OC2H5)C13, Ti(O n-C4Hg)C13, Ti(OC2H5)Br3 and Ti(O iso-C4~9)Br3; alkoxytitanium dihalides such as Ti(OCH3)2C12, Ti(OC2H5)2C12, Ti~O n-C4Hg)2Cl2 and Ti(OC2H5)2Br2; trialkoxytitanium monohalides such as Ti(OCH3)3Cl, Ti(OC2H5)3C1, Ti(O n-C4Hg)3Cl and Ti(OC2H5)3Br; and tetraalkoxytitaniums such as Ti(OCH3)4, Ti(OC2H5)4 and Ti(O n-C4Hg)4. Among them, the halogen-containing titanium compounds, particularly titanium tetrahalides, especially preferably titanium tetrachloride, are preferred. These titanium compounds may be used singly or as a mixture. Or they may be used as diluted in hydrocarbons or halogenated hydrocarbons.
In the preparation o~ the titanium catalyst component (A), the arnounts of the titanium compound, the magnesium compound the electron donor to be supported, and the other electron donors such as alcohols, phenols, rnonocarboxylic acid esters, the silicon compound and the aluminum compound which may used as required differ depending upon the method of preparation and cannot be defined in a general manner. For example, about 0.1 to ~ - ;
, ' ' , ' ~ : ' "'',':'`
12;~3~)0 about 10 moles of the electron donor to be supported and about 0.05 mole to about 1000 moles of the titanium compound may be used per mole of the magnesium compound.
In the present invention, a catalyst composed of the solid highly active titanium catalyst component composed of magnesium, titanium, halogen and a diester of a dicarboxylic acid prepared as above, (B) an organoaluminum compound and (C) an organosilicon compound of the formula R 3Si(OR ) is used.
Examples of the organoaluminum compound (B) include (i) organoaluminum compounds at least having an Al-carbon bond in the molecule, for example organoaluminum compounds r.epresented by the general formula R3mAl(OR4)nHpXq wherein each of R3 and R represents a hydrocarbon, for example a Cl-C15 hydrocarbon group, preferably Cl-C4 hydrocarbon group, X represents a halogen atom such as Cl, Br or I, O~m-3, O~n~3, 0-~p~3~ 0-q<3, provided that m+n+p~q=3, and (ii) complex alkylated products of aluminum and a metal of Group I of the periodic table represented by the following general formula MlAlR34 wherein ~1 is Li, Na or K, and R3 is as defined above.
Examples of the hydrocarbon groups for R3 and R4 are alkyl groups.
Examples of the organoaluminum compounds (i) are those of the general formulae R3 Al(OR4)3_m wherein R3 and R4 are as defined above, and m is preferably a number represented by ,:,^
. ` '' . .~
.
1`
lZ;~33l~
1.5-m-3, R mAlX3 m wherein R and x are as defined above, and m is preferably a number represented by O<m<3, R3mAlH3_m wherein R3 is as defined above, and m is preferably a number represented by 2-m<3, and R3mAl(oR4)nXq wherein R3 and R4 are as defined above, X is the same halogen as above, O<m-3, 0-n~3, O-q~3, m+n~q=3, Examples of the organoaluminum compounds (i) include trialkyl aluminums such as triethyl aluminum and tributyl aluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkyl aluminum alkoxides such as .
diethyl aluminum ethoxide and dibutyl aluminum butoxide;
partially alkoxylated alkyl aluminums such as alkyl aluminum sesquialkoxides (e.g., ethyl aluminum 2G sesquiethoxide and butylaluminum sesquibutoxide) and partially alkoxylated alkyl aluminums having the average composition represented by R2 5Al~OR2)o 5; dialkyl : aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide;
alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; partially halogenated alkyl aluminums9 ~or example alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; other partially hydrogenated alkyl aluminums, for example alkyl aluminum dihydrides . .~
,., ~ .: ..
~3~
such as ethyl aluminum dihydride and propyl aluminum dihydride; and partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxychloride, ethyl aluminum butoxy chloride and ethyl aluminl~m ethoxy bromide.
LiAl(C2H5)4 and LiAl(C7H15)4 may be cited as examples of the compounds (ii).
There may also be used organic aluminum compounds in which two or more aluminum atoms are bonded through an oxygen or nitrogen atom, which are similar to the compounds (i). Examples are (C2H5)2AlOAl(C2H5)2, (C4Hg)2AlOAl(C4H9)2, and (C2H5)2AlNAl(C2H5)2.
Of these, the trialkyl aluminums and ths alkyl aluminums in which two or more aluminum atoms are bonded are preferred.
The organosilicon compound (C) constituting the catalyst of this invention together with the components (A) and (~) described above is represented by the ~ollowing formula R 3Si(OR ).
In the formula, Rl and R each represent a hydrocarbon group having 1 to 5 carbon atoms, and the three ~1 groups may be identical or different.
Examples of the hydrocarbon group for Rl and R are alkyl, alkenyl, cycloalkyl, haloalkyl and alkoxyalkyl groups having 1 to 5 carbon atoms. Specific examples of the organosilicon compound (C) are trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propoxysilane, triethylmethoxysilane 9 tri-n-propylmethoxysilane, tri-iso-propylmethoxysilane tri-n-butylmethoxysilane, tri iso-butylmethoxysilane, tri-n-amylmethoxysilane and tri-iso-amylmethoxysilane.
In the present invention, 4-methyl-1-pentene is polymerized in the presence o~ the catalyst composed , -~ .
~2~23~
of the components (A), (B) and (C) described above.
Prior to the polymerization, a methylpentene is pre-polymerized in a hydrocarbon medium in the presence of the component (A), a part of the component (B) and a part of the component (C) to form about 1 to about 1000 g, per millimole of titanium in the component (A), of a polymer of the methylpentene. By performing the pre-polymerization, a powdery polymer having a high bulk density can be obtained in the subsequent slurry polymerization of 4-methyl~l-pentene. Accordingly, this offers the advantage that the performance of the slurry is good and the operation can be carried out at high polymer concentrations. Another advantage is that the amount of the polymer yielded per unit amount of the catalsyt is large, and a stereoregular polymer can be produced in a high proportion.
The methylpentene used in the pre-polymeriza-tion can be selected from 3-methyl-1-pentene, ~-methyl-l-pentene, 4,4-dimethyl-1-pentene, etc. Preferably, the pre-polymerization is carried out under relatively mild conditions and under such conditions that the pre-polymer obtained does not dissolve in the polymerization medium. For this purpose, the polymerization medium is preferably an inert hydrocarbon, for example an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, and an alicyclic hydrocarbon such as cyclopentane and cyclohexane.
In the pre-polymerization, it is preferred to use the titanium catalyst component (A) in an amount, calculated as titanium atom, of about 0.5 to aobut 1000 millimoles, particularly about 1 to about 10 millimoles per liter of the hydrocarbon medium. The organoaluminum compoudn (B) is used preferably in an Al/Ti atomic ratio of from about 1 to about 100, particularly from about 2 to about 20, and the organo-silicon compound ~C) is used preferably in an amount of .
, ~
:. . :
-, .
.... .... , :
3~
about 0.01 to about 2 moles, particularly about 0.02 to about l mole, per mole of the component (B).
I'he arnount of the methylpentene pre-polymerized is in the range of about l to about lO00 g, preferably about 3 to about lO0 g, per mi.llimole of the titanium in the component (~). The concentration of the methyl-pentene in the pre-polymerization is preferably not more than about l mole, especially not more than about 0.5 mole, per liter of the hydrocarbon medium.
Desirably, the pre-polymerization is carried out at a temperature at which the resulting pre-polymer does not dissolve in the hydrocarbon medium. The temperature varies depending upon the kind of the hydrocarbon medium, but is, for example, about -20C
to about -~70C, preferably about 0C to about 50C.
The pre-polymerization pressure may, for example, be atmospheric pressure to about lO kg/cm .
In the process of this invention, 4-methyl-l-pentene is polymerized or copolymerized by usin~ the catalyst subjected to the pre-polymerization treatment.
At this time, additional amounts o.f the component (B) and/or the component (C) may be supplied. Preferably, the component (B) i5 additionally used in an amount o~
about l to aobut lO00 moles, especially about lO to about 500 moles, per mole of the titanium and the component (C), in an amount of about 0.005 to about 2 moles, particularly about 0.01 to about l mole, per mole of the component (B).
When 4-methyl-l-pentene is to be copolymerized, ethylene and/or another alpha-olefin may be properly chosen. The comonomer may, for example, be an olefin having 2 to 20 carbon atoms other than 4-methyl-l-pentene such as ethylene, propylene, l-butene, l-pentene, l-pentene, l~hexene, 1-octene, l-decene, l-dodecene, l-tetradecene, l-octadecene and 3-methyl-l-pentene.
l`n the copolymerization, the proportion of the comonomer is desirably selected such ~hat the content of ..
12~ 0~
~ 17 -4-methyl-1-pen-~ene in the resulting copolymer becomes at least about 80 mole%, particularly at least about 90 mole %.
Polymerization of 4-methyl-1-pentene ls carried out preferably by the slurry polymerization techni-que. The polymerization medium may be 4-methyl-1-pentene itself, or an inert hydrocarbon such as those exemplified hereinabove for the pre-polymerization, The polymerization temperature maybe properly selected from those at which the slurry polymerization is possible. It varies depending upon the kind of the polymerization medium, but is preferably from about 20C to about 100C, preferably from about 30C to about 80C. It is preferred to employ a polymerization temperature higher (for example 9 at least about 5C
higher) than the temperature at which the prepolymeri-zation or pre-copolymerization is carried out. A
molecular weight controlling agent such as hydrogen may be used as required in order to control the molecular weight of the resulting polymer.
The polymerization pressure may, for example, be from atmospheric pressure to about 20 kg/cm2.
According to this invention, the yield of the polymer per unit amount of titanium is high, and the proportion of a stereoregular polymer formed is high.
In particularly, in the copolymerization of 4-methyl-1-pentene with ethylene and~or another alpha-olefin, the proportion of a solvent-soluble polymer formed is small, and the resulting copolymer shows a single melting point and has a narrow cornposition distribution.
The following Exarnples and Comparative Examples illustrate the present invention more specifically.
Example 1 Prep_ration of a titanium catalyst component (A) Anhydrous magnesium chloride (4~76 g; 50 mmoles), 25 ml of decane and 23.4 ml (150 mmoles) of 2-ethylhexyl alcohol were heated at 130C for 2 hours to .. : , :'~ ' ;~ ' :
.~:~ . ., :, "
i~Z3~
form a uniform solution. To the solution was added 1.11 g (7.5 rnmoles) of phthalic anhydride, and -the mixture was stirred at 130 C for 1 hour to dissolve phthalic anhydride in the uniform solution. The resulting uniform solution was cooled to room temperature, and added dropwise over 1 hour to 200 ml (1.8 moles) of titanium tetrachloride kept at -20C. After the addition, the mi~ture was heated to 110C over 4 hours.
When its temperature reached 110C, 2.68 ml (12.5 mmoles) of diisobutyl phthalate was added, and the mixture was maintained at this temperature for 2 hours with stirring. After the 2-hours reaction, the reaction mixture was hot-filtered to collect the solid portion.
The solid portion was again suspended in 200 ml of TiC14, and reacted again at 110C for 2 hours. After the reaction, the solid portion was collected again by hot filtration. It was fully washed with decane and hexane a-t 110C until no free titanium compound was detected from the washings. The titanium catlayst component (A) so prepared was stored as a hexane slurry.
A part of the component (A), however, was dried in order to examine its compoposition. It was found that the titanium catalyst component (A) contained 3.1% by weight of titanium9 56.0% by weight of chlorine, 17.0%
by weight of magnesium and 20.9% by weight of diiso-butyl phthalate.
Prepolymerization A 500 ml flask was charged with 200 ml of n-decane, 10 rnmoles of triethyl aluminum, 2 mmoles of trimethylmethoxysilane and 1 mmole, calculated as titanium atom, of the titanium catalyst component (A).
While maintaining a temperature of 25C, 30g of 4-methyl-l-pentene was added over the course of 60 minutes, and further reacted at 25C for 30 minutes. The reaction product was filtered by a glass filter, washed three times with 300 ml in total of n-decane, and again suspended in 200 ml of` n~decane. The amount of "` :
;:
~2;~3~
4-methyl-1-pentene pre-polymerized was 30 g per mmole of titanium.
P ymerization A l-liter au-toclave was charged with 500 ml of ~-methyl-l-pentene, C.5 mmole o~ triethyl aluminum, 0.05 mmole of trimethylmethoxysilane, 0.0025 mmole, calculated as titanium atom, of the pre-polymerization product, and 250 ml of hydrogen, and 4-methyl-1-pentene was polymerized at 50C for 30 minutes. Methanol was added to stop the polymerization. The polymerization product was filtered by a glass filter to separate it into a white powdery poly(4-methyl-1-pentene) and a sol~ent-soluble polymer.
The stereoregularity index (II) of the polymer was expressed as a percentage of a boiling n-heptane-insoluble portion based on the total amount of the polymer. The polymerization activity was expressed as grams of the entire polymer per mmole of titanium. The polymerization activity9 the II and the bulk density are shown in Table 1.
Comparative Example 1 4-Methyl-l-pentene was polymerized under the same conditions as in Example 1 except that the titanium catalyst component (A) was not subjected to the pre-polymerization treatment. The results are shown inTable 1. These results show the effects of the pre-polymerization.
Comparative Example 2 The same polymerization as in Example 1 was per~ormed except that diphenyldimethoxysilane capable of exhibiting high performance in the polymerization of propylene was used as the organosilicon compound. The results are shown in Table 1.
Comparative Example 3 The same polymerization as in Example 1 was carried out except that diphenyldimethoxysilane was used as the organic silicon compound in the pre-polymerization, . .
. , - ~, . -.. - .
- :
: : :
~2231~10 and trimethylmethoxysilane was used as the organosilicon compound in -the polymerization. The results are shown in Table 1.
Comparativ Example_4 The same polymerization as in Example 1 was carried out except that trimethylmethoxysilane was used as the organosilicon compound in the pre-polymerization, and diphenyldimethoxysilane was used as the organo-silicon compound in the polymerization. The results are shown in Table 1.
The results obtained in Gomparative Examples 3 and 4 show that the organosilicon compound of the ~ormula R13Si(OR2) is necessary both in the pre-polymeri-zation and the polymerization.
Examples 2 and 3 Example 1 was repeated except that the organosilicon compounds used in the polymerization and the prepolymerization were changed as shown in Table lo The results are also shown in Table 1.
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_ 21 rl ~) ~rl ~ l O r1 a) 0 0 O O
rl ~ E ~J 0 ~ ) 0 ~ ~
~, ::~ a) ~ o o o o o o o a)~ q~ ~_ E_ ____ __ __ . __ r OH _~ ~`U LO 1~
H ~ 0 (D rl ~ O ~ 0 S~_ a) co ~) .__ .__ .. _ _ 07h ~ rl O O O O O O O
~q) ~ ~rl O O O O O O O O
r~l E O :~ E O o ~ t` o ~ (o ~:~ r~ ~rl E-- ~ .. ..
U~r-l ~) ~) ~ ~rl ~ rl ~ (O
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I ~ I ~ I
O X O ~ I
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E ~ E .rEI E rl E
O ~ N ~ ~ rl ~) ~
~r~ r~l ~ r ~ r o E a) ~ o rl ~ - E ~ S (~ E ~S t~ ~ ~ 0 (~
r-l ~1) r~l rf ~-1 ~ Q~ rl rl rl Q~ rl rl rl rl rl r l rl ~q O h rl rl rl rl ~ rl rl rl ~ rl h rl Q~ E~ Q U~
~V_.
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U~ rl ~ r-l t~ t~
5 $-1 r ~ ~ rl rl E ~ X
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c~ S a~ o ~ a rl ~) 1 E a~ ~ ~ ~ E E a) rl O ~ Q rl ~ rl ~-1 rl .~1 ~ rl ~ O .rl ri rl h h U~ rl ~ E~
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.... ._ .. .
h I
a) O ~ a) r-l N ~r) r1 ~ r-l ~ r-l N
E ~ Q o E~ X ~ X X X X ~ -E ~ ~ ~ X 1~ 1 ~ X X
X ~1 0 ~1 X t) [s~ L1 ._ __ _ _ I
.'.~ ' :'` : f .. , ~. , ~: :
. .-'' : . :
~Z3~3~t Example 4 A l-liter autoclave was charged with 500 ml of ~-methyl-l-pentene, 10 ml of l-decene, 0.5 mmoles of triethyl aluminum, 0.05 mmole o~ trimethylmethoxy-silane, 0.0025 mmole, calculated as titanium atom, ofthe pre-polymerization product as prepared in Example 1, and 250 ml o~ hydrogen, and the rnonomers were polymerized at 50C for 30 minutes. Methanol was added to stop the polymerization. The polymerization product was filtered by a glass filter to separate it into a white powdery 4-methyl-1-pentene/1-decene copolymer and a solvent-soluble polymer. The polymerization activity, the amount of the solvent-soluble polymer and the decene content, the melting point and bulk density of the powdery copolymer are shown in Table 2.
The melting point was measured as follows by using DSC. The sampel was heated from room temperature to 280C, and then cooled from 280C to -20C. After this preliminary treatment, the sample was again heated and its melting point was measured. The rate of temperature elevation and lowering was 10C/min.
Comp _ a-tive Example 5 The same polymerization as in Example 4 was carried out except that the titanium catalyst component prepared in Example 1 was used without the pre-polymeriza-tion. The results are shown in Table 2. The results show the effec-t of the prepolymerization.
Com~arative Example 6 Example 4 was repeated except that diphenyl-methoxysilane was used as the organosilicon compound in the pre-polymerization and the polymerization. The results are shown in Table 2. The results show the e~fect of using the specific organosilicon compound.
Examples 5 and 6 Example 4 was repeated except that l-hexene or l-octadecene was used as the comonomer. The results are shown in Table 2.
': , '.. ' ~ ~ ' "
.. .. .
'' . :
:,. ~ -.: .
:.,.. -. . ., , : , :: :` . ,., ' : --,,~''- ~ , , :, .
:12Z3~V~
Examples 7 to 9 Exarnple 4 was repeated except tha-t trimethyl--ethoxysilane, triethylrnethoxysilane or tri-n-propylmethoxysilane was used as the organosilicon S compound in the pre-polymerization and the polymerization.
The results are shown in Table 2.
- .-'- '~ ~ :, , , , ' :; :, 3~
_ _ _ ___ ~___ _ ~ ) t\l~\J ^ t~l ~J~\J c\l N
~1 ~ 0 (\1 r~ I
~ Q~ N
O _ _ _ ~1 ~:: O O ~
N ~ h ~ t` O~D O a) O al~1 ,~ o ~ o a~ 3 (\J
h t~ O t) `~
o x ta E~ O ~ ~0 0 0 ::~ C -- o o o o o o o o m ~ ~_ ~ ~ O h ~_ ~0 ~ ~ p ~ ~ ~ t O t\l CL) O
u~ O ~ 1 3 C\l ~D o c~
~i ~ O O O`--~1 ~ O u~
~ I U~
. ~, ~) OO O O O O O O
E 0 5 O O O ~ O O O O
~ - ~
O ~d o ~ ~ ,1 ~ ~ C~J C~l _ P~ N td`--C
a~ ~0 ~ ~ ~ X g ~ O
E~ O I
~ ,1 ~ a ~ ~ ~_,I Q 1 O O ~ N S ~ C S S
O Q) ~d o S ~ ~ S au C a~ ~ o I X
O S N D. ~ ~ ~ O r~ ~ O ~ O
~-1h G~ O ~
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Claims (5)
1. A process for producing a polymer or copolymer of 4-methyl-1-pentene, which comprises polymerizing 4-methyl-1-pentene or copolymerizing 4-methyl-1-pentene with up to about 20 mole % of an olefin having 2 to 20 carbon atoms in the presence of a catalyst comprising (A) a solid highly active titanium catalyst component composed of magnesium, titanium, halogen and a diester of a dicarboxylic acid, (B) an organoaluminum compound, and (C) an organosilicon compound represented by the following formula R13Si(OR2) wherein each of R1 and R2 represents a hydrocarbon group with 1 to 5 carbon atoms, and the three R1 groups may be identical or different, wherein prior to the polymerization or copolymerization, a methylpentene is pre-polymerized or pre-copolymerized in the presence of a catalyst comprising the catalyst component (A), a part of the catalyst component (B) and a part of the catalyst component (C) to form about 1 to about 1000 grams, per millimole of titanium atom, of a methylpentene polymer or copolymer.
2. The process of claim 1 wherein the magnesium/
titanium atomic ratio of the catalyst component (A) is from about 2 to about 100.
titanium atomic ratio of the catalyst component (A) is from about 2 to about 100.
3. The process of claim 1 wherein the halogen/
titanium atomic ratio of the catalyst component (A) is from about 4 to about 100.
titanium atomic ratio of the catalyst component (A) is from about 4 to about 100.
4. The process of claim 1 wherein the diester/
titanium mole ratio of the catalyst component (A) is from about 0.2 to about 10.
titanium mole ratio of the catalyst component (A) is from about 0.2 to about 10.
5. The process of claim 1 wherein the pre-polymerization or pre-copolymerization is carried out at a temperature of about -20°C to about +70°C, and the polymerization or copolymerization is carried out at a temperature higher than the temperature of the pre-polymerization or pre-copolymerization.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP80,936/83 | 1983-05-11 | ||
| JP58080936A JPS59206418A (en) | 1983-05-11 | 1983-05-11 | Production of 4-methyl-1-pentene polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1223100A true CA1223100A (en) | 1987-06-16 |
Family
ID=13732343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000453668A Expired CA1223100A (en) | 1983-05-11 | 1984-05-07 | Process for production of 4-methyl-1-pentene polymer or copolymer |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4659792A (en) |
| EP (1) | EP0125910B1 (en) |
| JP (1) | JPS59206418A (en) |
| AT (1) | ATE22693T1 (en) |
| CA (1) | CA1223100A (en) |
| DE (1) | DE3460897D1 (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59117509A (en) * | 1982-12-24 | 1984-07-06 | Mitsui Petrochem Ind Ltd | Polymerization of olefin |
| US4525555A (en) * | 1983-01-14 | 1985-06-25 | Nippon Oil Company, Limited | Process for preparing polyolefins |
| JPH0723406B2 (en) * | 1985-07-16 | 1995-03-15 | 三菱油化株式会社 | Method for producing propylene polymer |
| JPH075675B2 (en) * | 1985-10-01 | 1995-01-25 | 三井石油化学工業株式会社 | 4-methyl-1-pentene random copolymer |
| JPH06104693B2 (en) * | 1986-01-06 | 1994-12-21 | 東邦チタニウム株式会社 | Catalyst for olefin polymerization |
| JPH0735410B2 (en) * | 1986-01-31 | 1995-04-19 | 三菱油化株式会社 | Catalyst for stereoregular polymerization of olefins |
| US4798866A (en) * | 1986-07-14 | 1989-01-17 | Mitsui Petrochemical Industries, Ltd. | Branched alpha-olefin polymer composition and process for its production |
| JPH0723412B2 (en) * | 1986-09-04 | 1995-03-15 | 住友化学工業株式会社 | Process for producing 4-methylpentene-1 copolymer |
| US4814314A (en) * | 1986-09-26 | 1989-03-21 | Mitsubishi Petrochemical Company Limited | Catalyst for olefin polymerization |
| JP2546258B2 (en) * | 1987-03-11 | 1996-10-23 | 日本合成ゴム株式会社 | Process for producing elastomeric long-chain α-olefin polymer |
| US6121393A (en) * | 1987-02-17 | 2000-09-19 | Mitsui Chemicals | Process for polymerizing alpha-olefins |
| CA1310955C (en) * | 1987-03-13 | 1992-12-01 | Mamoru Kioka | Process for polymerization of olefins and polymerization catalyst |
| ES2052004T5 (en) * | 1988-06-17 | 2002-05-16 | Mitsui Chemicals Inc | POLYOLEFINE PREPARATION PROCEDURE AND POLYMERIZATION CATALYST. |
| JPH0232106A (en) * | 1988-07-20 | 1990-02-01 | Mitsui Petrochem Ind Ltd | Production of 4-methyl-1-pentene copolymer |
| JP2695192B2 (en) * | 1988-08-03 | 1997-12-24 | 三菱化学株式会社 | Method for producing propylene polymer |
| US5206315A (en) * | 1989-04-10 | 1993-04-27 | Phillips Petroleum Company | Process for polymerizing 1-olefins and catalyst therefor |
| JP2850427B2 (en) * | 1989-12-25 | 1999-01-27 | 東ソー株式会社 | Method for producing polyolefin |
| FI87575C (en) * | 1990-02-20 | 1993-01-25 | Neste Oy | REFERENCE FORMING A FRAME STEERING CATALYTIC CONVERTER, REFERENCE FORMING A POLYOLEFIN GENOM ATT ANVAENDA SIG AV DENNA CATALYST SAMT PRODUCT SOM FRAMSTAELLTS MED DETTA FOERFARE |
| US5726262A (en) * | 1990-04-13 | 1998-03-10 | Mitsui Petrochemical Industries, Ltd. | Solid titanium catalyst component for olefin polymerization, olefin polymerization catalyst, prepolymerized polyolefin-containing catalyst and method of olefin polymerization |
| US5115054A (en) * | 1990-10-12 | 1992-05-19 | Phillips Petroleum Company | Catalysts containing poly(3-ethyl-1-hexene) and uses thereof |
| US5182330A (en) * | 1991-08-13 | 1993-01-26 | Phillips Petroleum Company | Process for the copolymerization of 4-methyl-1-pentene |
| RU2152421C1 (en) * | 1994-05-19 | 2000-07-10 | Мицуи Петрокемикал Индастриз Лтд. | METHOD OF PURIFICATION OF α-OLEFINS FOR POLYMERIZATION AND METHOD OF SYNTHESIS OF POLY-α-OLEFINS |
| RU2225415C2 (en) * | 1999-04-15 | 2004-03-10 | Базелль Текнолоджи Компани Б.В. | Olefin polymerization components and catalysts |
| JP4828415B2 (en) * | 2004-06-10 | 2011-11-30 | 三井化学株式会社 | Olefin polymer and use thereof |
| US8975353B2 (en) * | 2004-11-17 | 2015-03-10 | Mitsui Chemicals, Inc. | Solid titanium catalyst component, olefin polymerization catalyst, and process for producing olefin polymer |
| KR20070091444A (en) * | 2006-03-06 | 2007-09-11 | 주식회사 엘지화학 | Polymerization method of propylene comprising olefin pre-polymerization step |
| US20090161045A1 (en) | 2006-05-01 | 2009-06-25 | Mitsui Chemicals, Inc. | Method of Compensating Wavelength Dependence of Birefringence of Optical Part, Optical Part, and Display Obtained with these |
| WO2010024286A1 (en) | 2008-09-01 | 2010-03-04 | 三井化学株式会社 | Ionomer resin, resin compositions containing same and uses of both |
| US10345355B2 (en) | 2013-03-31 | 2019-07-09 | Ziota Technology Inc. | Method of communication between distributed wire harness test units using wire under test |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5330681A (en) * | 1976-09-02 | 1978-03-23 | Mitsui Petrochem Ind Ltd | Preparation of polyalpha-olefin |
| JPS588686B2 (en) * | 1978-12-01 | 1983-02-17 | チッソ株式会社 | Method for producing α↓-olefin polymer |
| JPS603324B2 (en) * | 1978-12-28 | 1985-01-28 | 三井化学株式会社 | Method for producing ethylene copolymer |
| JPS5825362B2 (en) * | 1980-02-15 | 1983-05-27 | チッソ株式会社 | Method for producing α-olefin polymer |
| JPS56129206A (en) * | 1980-03-14 | 1981-10-09 | Chisso Corp | Production of alpha-olefin polymer |
| JPS56133303A (en) * | 1980-03-22 | 1981-10-19 | Chisso Corp | Production of alpha-olefin polymer |
| IT1209255B (en) * | 1980-08-13 | 1989-07-16 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE. |
| JPS5880937A (en) * | 1981-11-06 | 1983-05-16 | Matsushita Electric Ind Co Ltd | Voice switch call device |
| JPS5883006A (en) * | 1981-11-13 | 1983-05-18 | Mitsui Petrochem Ind Ltd | Polymerization of olefin |
-
1983
- 1983-05-11 JP JP58080936A patent/JPS59206418A/en active Granted
-
1984
- 1984-05-07 CA CA000453668A patent/CA1223100A/en not_active Expired
- 1984-05-11 DE DE8484303227T patent/DE3460897D1/en not_active Expired
- 1984-05-11 EP EP84303227A patent/EP0125910B1/en not_active Expired
- 1984-05-11 AT AT84303227T patent/ATE22693T1/en not_active IP Right Cessation
-
1985
- 1985-12-23 US US06/814,166 patent/US4659792A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0125910A1 (en) | 1984-11-21 |
| US4659792A (en) | 1987-04-21 |
| EP0125910B1 (en) | 1986-10-08 |
| JPS59206418A (en) | 1984-11-22 |
| DE3460897D1 (en) | 1986-11-13 |
| ATE22693T1 (en) | 1986-10-15 |
| JPH0354687B2 (en) | 1991-08-21 |
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